Process for the conversion of fluid reactants



Sept. 17, 1946.

Filed June 26, 1944 L. C. 4HUFF PROCESS FOR THE CONVERSION OF FLUID REACTANTS aaw I Patented Sept. 17, 1946 PROCESS FOR THE CONVERSION F FLUID REACTANTS Lyman C. Huff, Chicago, Ill., assignor to Universal Oil Products Company, Chicago, Ill., a corporation of Delaware Application June 26, 1944, Serial No. 542,210

Claims.

This is a continuation-in-part of my co-pending application Serial Number 530,645, filed April 12, 1944.

The invention is directed to an improved method and means for effecting the conversion of fluid reactants in the presence of a mass of subdivided solid contact material which becomes contaminated with deleterious products of the conversion reaction and `is regenerated by removing the 4deleterious contaminants. The process is of the type in which the conversion step and the regenerating step are conducted continuously andsimultaneously in separate confined reac tion and regenerating -zones between and through which the subdivided solid contact material is continuously circulated.

The process and apparatus are particularly acl- 1 vantageous as applied to hydrocarbon conversion reactions, such as catalytic cracking, reforming, dehydrogenation, dehydrocyclization or aromatization `and the like, in which `the `Contact material .comprisescatalyst which promotesthe de` dusty nature should be avoided so that they will not excessively iill the voids between the larger particles and give an excessive pressure drop `for `the reactants and regenerating gases passing through the beds. For this reason, the particles charged to the system are preferably of substantially uniform or well graded size and any excessive quantity of nes produced by attrition of the larger particles within the system is'preferably removed from the system and replaced by larger particles. To avoid excessive attrition, the particles should have good structural strength. The use of substantially spherical particles will also greatly assist in avoiding excessive attrition. One suitable method of preparing synthetic catalysts which may be advantageously usedin the present process is disclosed lin application Serial Number 516,392 of Glenn M. Webb and Reno W. Moehl, led December 3l, 1943.

A special feature of the invention resides in the manner andrmeans whereby continuous circulation of the solid particles of catalyst or contact material is effected through the system. Their circulation is effected, in part, by gravitational descent from a separating zone and hopper mounted above the reaction and regenerating vessels serially through these vessels, and, in part, by Vdischarging the solid particles from the lower 4vessel of .the series into a gas-lift transfer line cal or-of other regular Aor irregular shape, is fsufficient-ithat the particles will `not` compact eX-f cessively togivea high `pressure drop when beds of substantial depth are employed in the reacf,r tion` and regenerating zones. YIt is a further re--` quirement that the `solid particles be suiiiciently small to facilitate their transportation bygasliftiin a part of Ythe circuit through which they flow between the reaction `and rregenerating ves` ties of excessivelyne vparticles of a powdery or of ythe solid particles to be trans- Wherein they are commingled with transporting fiuid and carried-upwardly by the latter into thel aforesaid separating zone andhopper to complete the circuit.l The solid particles pass downwardly from the hopper through the contacting vessels in the form of a continuous and uninterrupted relatively compact column. vBy eliminating intermediate feeding Vdevices and the like i which wouldinterrupt the -continuity of 'the column, the height ofr the latter imposes a substan- .tial pressure on the solid particles `at the bottom oi'ithe column which is materially greater than the Ygas or vapor pressure prevailing above the column in the separating Zone Yand hopper. In

the gas-lift transfer line through which the vsolid particles are'tran'sported from the lower contact.-

ing vessel Vof the series back to the separating Zone and hopper, the particles are suspended in the transporting fluid so that there is little vor no accumulative `weight ofVV solid particles in the height of the gas-lift .transfer line and they flow upwardly with the transporting fluid .to the -rela As another special feature of the invention I prefer to employ vaporous and/or gaseous products discharged from the reaction Zone as the transporting fluid for the solid particles in the gas-lift transfer line. As applied to the conversion of normally liquid products, such as, for example, the catalytic cracking of hydrocarbon oil, this use of outgoing Vaporous conversion products as transporting fluid is advantageous in that. suiicient pressure can be developed in the Vaporous stream of out-going conversion products to permit its use as transporting fluid by pumping the charging oil being supplied to the reactor in liquid state, which is materially less expensive than employing a gas compressor or the like to develop suicient pressure in the stream of transporting fluid, as would be necessary when employing incoming or outgoing regenerating gas or gas from an external source as the transporting fluid. c

Although the features of the invention are advantageously applicable to the conversion or treatment of fluid reactants generally in the presence of a mass Vof subdivided solid contact material, catalyst or`reagent, they are, as previously mentioned, particularly advantageous as applied to the catalytic conversion of fluid hydrocarbons and, for the sake of being more explicit in illustrating therfeatures and advantages of the invention, the succeeding description will b-e directed principally to an operation in which hydrocarbon oil is catalytically cracked.

The accompanying diagrammatic drawing is an elevational View,` shown principally in section; of one specic form of apparatus embodying the features of the invention and in which the improved process provided by the invention may be successfully conducted.`

Y Referring now to the drawing and to the flow through the system illustrated, the catalyst particlesare collected, as will be later described, within the separating vessel and hopper I in the form Vof a relatively compact bed 2. The catalyst particles collected in bed 2 will have accumulated deleterious heavy combustible Yproducts of the cracking or hydrocarbonv conversion reaction being conducted within the system.A All or a major portion of these combustible deposits are to be burned from the catalyst particles in the regenerating step, as will be later described. In addition, the bed 2 contains occluded and adsorbed transporting gas in which the solid particles were transported to vessel I. When, as in 4 stripping gas, such as steam, for example, which is supplied to the lower portion of the stripper through line 6 and valve 'I and is distributed substantially uniformly over the cross-sectional area of bed by a suitable distributing member 8 provided within the lower portion of the stripper. The Stripped-out volatiles and stripping gas are discharged'from the. upper extremity of bed 5 into the space 9 provided thereabove within vessel 5 and are thence discharged through line IE) and valve I I to suitable separating and recovery equipment, not illustrated. This separating and recovery equipment may conveniently comthe? case illustrated, outgoing vaporous and gasecus products ofv the hydrocarbon conversion'reaction are employed as the transporting Huid,V the occluded and adsorbed vapors and gasesare o f alpvaluble nature and if not removed and recovered would be lost by burning inthe succeeding regenerating step. Furthermore,` their combustion in the regenerator would develop'additional heat in this step, which is ordinarily undesirable. l will destroy or permanently impair its activity In view'of the inclusion of Valuble light hydrocarbons in the bed 2 of solid particles accumu-1 lated in vessel I, a stripping vessel 3 is interposed between this hopper and the regenerator wherein occluded and adsorbed volatile hydrocarbons are substantially-removed from the solid particles before they enter the regenerator. particles pass downwardly from the lower, hopper-like portion of Vvessel I vthrough-conduit VIl into the upper portion of stripper 3. 'Here they' pass down'wardlythrough anotherrelatively compact bed 5 of the solid particles maintained in thiszone countercurrent to a stream of suitable .The solid:

erat'ed vcatalyst p asses about the (,istrilc'lutingV member I 'l in the lower portion of the regeneratorf into the substantiallyconical bottom sectionv of' Excessive heating of the'ca'talystwprise the same fractionating equipment to which Vaporous and gaseous hydrocarbon conversion products of the process are supplied, as will be later described.4

The stripped catalyst particles pass downwardly about member 8 into the conical lower section of stripper 3 and are thence directed through conduit l2 into regenerator I3 wherein they move downward through the relatively compactY bed I4 maintained in this zone. Air or other suitable oxygen-containing gas is supplied to the regenerator through line I5 and valve I6 and is distributed substantially uniformly over the horizontal cross-section of bed Ill by means of a suitable distributing memberl'l from which it passesupwardly into bed I4. l taminants are burned from the solid catalyst particles by their contact vwith Vthe oxidizing gas passing countercurrent -thereto through bed I4. Resulting gaseous'productsof combustionl are discharged from the upper 'extremity of bed I4- into a-space provided thereabove within the regenerator, from which they are directed through line 51 and valve 58, preferably to suitable heat` recovery equipment of any desired form not 'illustrated.

A substantial portion of the heat developed by burningv the combustible contaminants inthe' regenerating step is stored in the solid catalyst particles dischargedY from the lower portionfof this zone. The stream'or column of catalyst particles passing from the regenerator will also containy entrained and adsorbed gasesl comprising a part of the regenerating gas employed and resulting stantially stripped of such material and, in they case illustrated, a stripper IS similar ,in form to` stripper 3 above mentioned'is interposed between the regenerator and the reactor. The hot regenthis vessel and isthence` directed through conduit I9 into and throughY the relatively compactV bedz 20 vof catalyst particlesmaintained.within, stripper I8. Steam or other suitable stripping gas isl supplied to the lower portion of stripper-l8 through line 2| and-valve 22 to be distributed:to`

bed I4 by member 23 disposed within the lower portion of the stripping vessel and to pass up-f wardly from member 23 through bed 20 countercurrent to the descendingsolid particles.Re--

Vsulting stripping gas and stripped-out gases areV discharged from the upper portion of bed `20 into the space 23 provided thereabove within the stripper and are-thence discharged through line 25- and va1ve'26, preferablyito the same heat re-jj'. r covery equipment to whichcombustion gases, are, n

Combustible con- 5 discharged,- as previously-'f mentioned, from re` generator I3.

The substantial-ly stripped catalyst particles pa-ssdownwardlyL about distributing member 23T` into thi,y cone-likelower-i section of stripper' I8l` and are thencedischarged? through conduit 2-11 into reactor 28 to pass downwardly through the relativelyf compactl bed 9l ot catalyst.. particles maintained within this zone.

Fluid reactants' to be converted, which, in the.- case-illustrated, comprise hydrocarbon oil to be cracked; are supplied in' liquid state through line 59"' and valve 30i to pump l-l'-f wherefronr they are.

wardly into bedf 29= andi are convertedlbyf counter.-Y current contactwith thev catalyst particles pass'-A ingthrough the bed: Resulting vaporous@ and.

gaseous con-version4 products* are discharged-from theA upper extremity ofi bedi 2l);i into the space 31. provided" thereabove within the reactor, from which` they' are discharged; through l line'A 38V and. may pass, in part, through valve t9E in this-line to suitable fractionating and recovers7J equipment. of` any desired conventional form-5 notillustrated'.

The temperature of' the catalyst is reduced.

actor"` by giving up heat to the endothermichyd-rocarbon conversion reaction-which it promotes.. and the catalyst particlesi accumulate deleteriousy comloustiblecontaminants comprising heavy products or the hydrocarbon'conversion reaction; To-restore its activityrand heatl content the-:catas lysteis1L returned from thereactor to4 the regen-` crater;A thusd4 settingV up a cyclicV now' ofcatalystv through the system.

Thepartially cooled' and-contaminated catalyst passes downwardly about distributingj member 36v in the lower portion off theL reactor' into: the. cone-like-'lower sectionof thisfvessel and is -thenca directed through conduit 4c* and through an adi@- justa-ble orifice or flow-regulating valve 4l. provided in conduit tu adjacent its lowerI end into'.`

a substantially straight upwardly extending: gasl-y lift'transieriline)42. In line 42 the catalyst par:-A ticlesf are commingl'ed with i and suspended` inH a' streamoi? transportingliiuid.'v which., in the. caserV illustrated, comprises all or a portion of thezvae porous` and gaseous conversion products discharged' from reactor 281- Thef conversion prodiucts` to beI used'astransportin'g fluid' arel directed from line-38Av under the vaporior gas pressure prevailing within theA reactor above bed 29 through line 4A3and4 valve Mintotransfer'line 42..

The vaporor gasfpressure maintained invessel If abovei'helbed 2 is materially less than .thestaticr pressure developed inthe relatively compact column of catalyst particles above the adjustable: orifice or flow-regulating valve. 4I in line 4E!" and thevapor or gas' pressure maintained' in space 31 withinthe reactor-is suiiiciently greater than that prevailinginthe space above bed 2 in Vessel' I to overcome the pressure dropA in the stream of transporting gas as vit passes through line 38, line 43 andgas-liit transfer line 42 so that thetransporting gas and the catalyst particles suspended therein fiow upwardly throughA thegas-liftv transfer'line42- into'the disengagi-ng space 45- provided within vessell above bedZ. i v

GSL

The` Velocity off the'L transportingI gas-isV materiallly reducedfiim space 45ofthelseparatingvesseh l` as compared with its: velocity in line `412 ssoithat'. all or.' a substantialfportion ofithescatalyst1-pamticles separate by gravity from-the; transporti'ng` gas-Hin; vessel-L I and: collect. in:` thelower` portion oij thiszone toitormthefbed 2 The; transportinggas, which, as` previously mentioned. comprises; vaporous: andi gaseous hydrocarbon conversion products, ircthe case! illustrated, is-directed from the upper: portionzof; vessel l" through. line y 4&landi valvesA t1. to suitable fractionating and recoveryequipment of any desired conventional? form: which is not"- pertinent; totr the present inyentiom and isl therefore not. illustrated;` When.` desireciv and as: previously indicated, that: quantity' of: they vaporous: and'l gaseous conyersion:products:diseV chargedfrom-k reactor' 2B which may notl'b'@ re-V quired as; transporting' huid; in; transiter.1 :line: 425: may beV directed. throughl valve 3a in linel 3.8l to; the; sameV fractionating. and:` recovery r equipmentl to which the vapors and gases.utilizedyas':transf` porting fluid are directed from vessel Il.

Adjustment. of theoriiice or opening through the flow-regulating; Valvea 4 I in` conduit', 40 regu:`

lates the: rate. aty which catalyst particles arefcirsculated through the. system. andxthis rate; mayI be adjusted. to suit requirementsrso asjtogivefthedesired residence time` for the catalyst; inv therA reaction and regeneratingi'izonesiand; give the cle--` sired catalysteoil ratioin. the, reactor-A and` the. desired ratio of catalyst toi the; regenerating,` gas.

in theregenerator.v The-term catalyst-oilratiof as here used refers to the-,poundsiof catalyst-...ven

. tering theV reaction, zone. per,` hour,` per pound ot.

y regenerator and the average 'temperature ofthe catalyst passing through the, reactor. When this results in a regenerator temperature, which is relatively close` to the reaction temperaturev desi'red it is unnecessary to supply additional'heat to or abstract additional heat from the catalystas it circulates through the, system'. However, as applied to reactions such as catalytic crackL ing in an operation producing commercially practical yieldsof the desiredproducts; the quarrtity of"combustible depositsV accumulated by the catalyst in the reaction step andV` burn-edi there'- from in, the regenerating step is usually" more than that required tostore in the4 catalystall of' the heat necessary for conductingl the-hydro-- carbon conversion reaction. I thereforeV provid(am for abstracting excess-heat from the catalyst, when desired. This maybe done; as'intvhel case: illustrated, either after the` catalyst leaves the reactor and before it' enters'the regenerator or4 after the catalyst leaves the regeneratorandbe fore it enters thev reactor or, in part, by'both..

In the caseillustrated, a. cooling coil 48` isfpro-L vided in theY lower portionf of vessel I` througlr which a suitable cooling iiuid, Such as steam, water,v oil` or the likel is: passed via lines-:.491 and 5i] in an amountcontrolled by valve. '5l to: abs.1 stract the desired quantity ot heat from the; catF al'yst passing through. bed 2. Alternatively, a. cooler'of any suitableiorm maybe.` interposed conduit `lll), .transfer-l line` l 42 or in conduits 4.` or'` |2vor1n stripper 3, for the purpose of controllably reducing the temperature of the catalyst being suppliedlto the regenerator from the reactor and thus reducing the average temperature obtained inthe regenerator.

The drawing also illustrates the provision of a suitable cooler 52 in conduit 21 and provision for passing suitable cooling fluid such as steam, water, oil or the like through this cooler in indirect contact and heat transfer relation with the catalyst passing from the regenerator to the reactor.- Cooling fluid is supplied to cooler 52 through line 53 and is discharged therefrom through line 54 inamounts regulated by valve 55.` Alternatively; a suitable cooler may be located in conduit I9 or in the stripping vessel I8 for-controllably reducing the temperature of the catalyst supplied to therreactor from the regenerator, in case the temperature prevailing in the latter zone is considerably higher Athan the tem,-` perature at which it is desired to conduct the conversion reaction.'

I claim: Y

1.'.The process of converting Vfluid reactants in'the presence of a mass of subdivided solid contact material which comprises directing the solid contact material downwardly in series from an uppermost separating zone through separate confined 4reaction and regenerating zones, maintaining' a relatively compact bed of the solid particles' in each of said zones and maintaining thel downwardly moving solid particles in the `form of a continuous relatively compact column extending uninterruptedly through and between said'zonesthe static pressure at the bottom of said column being substantially greater than the` pressure in said uppermost separating zone, contacting the bed of solid particles in the regenerating zone with regenerating gas to remove therefrom deleterious contaminants accumulated in the reaction zone, contacting the bed of solid particles in the reaction zone vwith the iiuid reactants to be converted and effecting their `conn version therein, maintaining the pressure of the vaporous conversion products in said reaction zone greater than the pressure in said separating zone, separately removing uid products of regeneration and fluid products of the conversion reaction from the respective regenerating and reaction zones and preventing any substantial commingling thereof, discharging the subdivided solidparticles at said static `pressure from the bottom of said continuous column into and suspending the same in a stream of transporting fluid comprising a portion of said vaporous conversion products, directing the suspended particles solely by the gas-lift action of said transporting fluid upwardly into said separating zone, thevpressure of said vaporous conversion products in said reaction zone being sufciently greater than the pressure ,in said separating zone to overcome the pressure drop of said transporting uid during its flow from said reaction zone tosaid separating zone, separating` said trans` porting uid from at least a major portionof the subdivided solid particles and ldirecting the latter downwardly as aforesaid through the con-Y tacting zones.- c

2. A process such as defined in claim 1, wherein said fluid reactants to be converted are supplied to the reaction zone by pumping them while in liquid statey and wherein iiuid conversion products are discharged in essentially vaporous state and at .-superatmospheric pressure; from the 'reaction zone and utilizedv at least in part as said transporting fluid. f l

3. A process such as dened in claim 1wherein said conversion reaction comprises the catalytic crackng'of normally yliquid hydrocarbons and the subdivided solid contact material comprises cracking catalyst.

- 4. The process of endothermically converting normally liquid hydrocarbons in essentially vaporous state and in the presence of subdivided solid catalyst which promotes the conversionvre-4 action comprising imposing asuperatmospheric pressure on the hydrocarbons in liquid state and substantially heating the same to eiect their substantial vaporization, supplying the heated, vapors to a conned reaction zone'and into con'- tact with a relatively compact bed of downwardly movingi catalyst particles maintained therein, therein eiecting their conversion and discharging resulting vaporous conversion productswhile still under superatmospheric pressure from the upper portion of the reaction zone, separately discharging catalyst particles from the lower portion of said reaction zone andsuspending the same in transporting vapors comprising a portion of said vaporous conversion products, directing the resulting suspension solely by the gas-lift action of said portion of vaporous conversion products into a separatingr zone of substantially reduced pressure disposed at a substantal elevation above the reaction zone, said superatmospheric pressure of said vaporous conversion products being sufficiently greater than said reduced pressure in said separating -zone to overcome'the pressure drop of the transporting vapors during their flow'from said reaction zone to said separating zone, separating catalyst particles from the transporting vapors and collectf ing the catalyst particles in the form' of a relatively compact bed, directing catalyst particles fromjthe last named bed downwardly into a separate confined regenerating zone, therein maintaining another relatively compact bed of catalyst particles and burningtherefrom com.

bustible 4contaminants accumulated in Ythe reaction zone by passing oxidizing gas upwardlyv tially greater than the pressure in said separat-f ing zone, and effecting the discharge of catalyst particles from the lower portion of the reaction zone into said transporting vapors under the weight of said continuous column.

"5. A conversion processwhich comprises passing subdivided solid contact material vertically downward in the form of a relatively compact continuousV column extending uninterruptedly from anuppermost separating zone through and between a plurality of superimposed contacting zones, the lstatic pressure at the bottom' of said column being substantially greater than the pressure in said uppermost separating zone, contacting a hydrocarbon reactant under Yconversion conditions with the solid material in one of the last-named zones while maintaining the pressure of the vaporous conversion products therein sul@v stantially greater than the pressure in said separating zone, regenerating the solid material in another of the contacting zones oy passing an oxygen-containing gas therethrough, discharging solid particles from the bottom of said continuous column into a stream of transporting fluid comprising Vaporous conversion products of said hydrocarbon reactant under the weight of the column and directing the same upwardly into said separating zone solely -by the gas-lift action of 

